|Publication number||US6315886 B1|
|Application number||US 09/206,924|
|Publication date||Nov 13, 2001|
|Filing date||Dec 7, 1998|
|Priority date||Dec 7, 1998|
|Also published as||US6328875|
|Publication number||09206924, 206924, US 6315886 B1, US 6315886B1, US-B1-6315886, US6315886 B1, US6315886B1|
|Inventors||Guillermo Daniel Zappi, Norman L. Weinberg|
|Original Assignee||The Electrosynthesis Company, Inc.|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (41), Non-Patent Citations (4), Referenced by (135), Classifications (39), Legal Events (7)|
|External Links: USPTO, USPTO Assignment, Espacenet|
The present invention relates generally to the purification of aqueous solutions, and more specifically, to electrochemical methods and more efficient and safer electrolytic apparatus for the destruction of pollutants in drinking water, industrial waste waters and contaminated ground water.
Wastewater can be a valuable resource in cities and towns where population is growing and water supplies are limited. In addition to easing the strain on limited fresh water supplies, the reuse of wastewater can improve the quality of streams and lakes by reducing the effluent discharges they receive. Wastewater may be reclaimed and reused for crop and landscape irrigation, groundwater recharge, or recreational purposes.
The provision of water suitable for drinking is another essential of life. The quality of naturally available water varies from location-to-location, and frequently it is necessary to remove microorganisms, such as bacteria, fungi, spores and other organisms like crypto sporidium; salts, heavy metal ions, organics and combinations of such contaminants.
Over the past several years, numerous primary, secondary and tertiary processes have been employed for the decontamination of industrial wastewater, the purification of ground water and treatment of municipal water supplies rendering them safer for drinking. They include principally combinations of mechanical and biological processes, like comminution, sedimentation, sludge digestion, activated sludge filtration, biological oxidation, nitrification, and so on. Physical and chemical processes have also been widely used, such as flocculation and coagulation with chemical additives, precipitation, filtration, treatment with chlorine, ozone, Fenton's reagent, reverse osmosis, UV sterilization, to name but a few.
Numerous electrochemical technologies have also been proposed for the decontamination of industrial wastewater and ground water, including treatment of municipal water supplies for consumption. While growing in popularity, the role of electrochemistry in water and effluent treatment heretofore has been relatively small compared to some of the mechanical, biological and chemical processes previously mentioned. In some instances, alternative technologies were found to be more economic in terms of initial capital costs, and in the consumption of energy. Too often, earlier electrochemical methods were not cost competitive, both in initial capital costs and operating costs with more traditional methods like chlorination, ozonation, coagulation, and the like.
Earlier electrochemical processes required the introduction of supporting electrolytes as conductivity modifiers which adds to operating costs, and can create further problems with the disposal of by-products. Electrochemical processes in some instances have been ineffective in treating solutions by reducing concentrations of contaminants to levels permitted under government regulations. Heretofore, such electrochemical processes have often lacked sufficient reliability for consistently achieving substantially complete mineralization of organic contaminants, as well as the ability to remove sufficient color from industrial waste waters in compliance with government regulations.
Notwithstanding the foregoing shortcomings associated with earlier electrochemical technologies, electrochemistry is still viewed quite favorably as a primary technology in the decontamination of aqueous solutions. Accordingly, there is a need for more efficient and safer electrochemical cell configurations and processes for more economic treatment of large volumes of industrial waste waters, effluent streams and contaminated ground water, including the decontamination of municipal water supplies making them suitable for drinking.
The present invention relates to improved means for electropurification of aqueous solutions, particularly effluent streams comprising waste waters polluted with a broad spectrum of chemical and biological contaminants, including members from such representative groups as organic and certain inorganic chemical compounds. Representative susceptible inorganic pollutants include ammonia, hydrazine, sulfides, sulfites, nitrites, nitrates, phosphites, and so on. Included as organic contaminants are organometallic compounds; dyes from textile mills; carbohydrates, fats and proteinaceous substances from food processing plants; effluent streams, such as black liquor from pulp and paper mills containing lignins and other color bodies; general types of water pollutants, including pathogenic microorganisms, i.e., bacteria, fungi, molds, spores, cysts, protozoa and other infectious agents like viruses; oxygendemanding wastes, and so on.
While it is impractical to specifically identify by name all possible contaminants which may be treated successfully according to the claimed methods, it will be understood that language appearing in the claims, namely “contaminated aqueous electrolyte solution”, or variations thereof is intended to encompass all susceptible pollutants whether organic, inorganic or biological.
The electropurification methods and apparatus for practicing this invention are particularly noteworthy in their ability to effectively purify virtually any aqueous solution comprising one or more organic, certain inorganic and biological contaminants present in concentrations ranging from as low as <1 ppm to as high as >300,000 ppm.
Only electricity is required to achieve the desired chemical change in the composition of the contaminant(s), in most cases. The conductivity of tap water is sufficient for operation of the improved cell design. Hence, it is neither required, nor necessarily desirable to incorporate additives into the contaminated aqueous solutions to modify the conductivity of the solution being treated to achieve the desired decomposition of the pollutant/contaminant. Advantageously, in most instances solid by-products are not produced in the electropurification reactions as to create costly disposal problems. The improved electrochemical processes of the invention are able to achieve complete or virtually complete color removal; complete mineralization of organic contaminants and total destruction of biological pollutants even in the presence of mixed contaminants, and at a cost which is competitive with traditional non-electrochemical methods, such as chlorination, ozonation and coagulation, and thereby meet or exceed government regulations.
Accordingly, it is a principal object of the invention to provide an electrolysis cell which comprises at least one anode and at least one cathode as electrodes positioned in an electrolyzer zone. The electrodes are preferably spaced sufficiently close as to provide an interelectrode gap capable of minimizing cell voltage and IR loss. Means are provided for directly feeding the contaminated aqueous electrolyte solution to the electrodes for distribution through the interelectrode gap(s). Means are provided for regulating the residency time of the aqueous electrolyte solution in the electrolyzer zone for modification of contaminants ether electrochemically by direct means and/or by chemical modification of contaminants to less hazardous substances during residency in the cell. Additional means are provided for collecting decontaminated aqueous electrolyte solution descending from the electrolyzer zone. It is also significant, the electrolysis cell according to the invention has an “configuration”.
In addition to the electrochemical cell of this invention, further means are provided for practical and efficient operation, directly feeding contaminated aqueous electrolyte solution to the cell by pump means or by gravity; pretreatment means for the contaminated aqueous electrolyte solutions, for example, means for aeration, pH adjustment, heating, filtering of larger particulates; as well as means for post-treatment, for example, pH adjustment and cooling, or chlorination to provide residual kill for drinking water applications. In addition, the invention contemplates in-line monitoring with sensors and microprocessors for automatic computer-assisted process control, such as pH sensors, UV and visible light, sensors for biological contaminants, temperature, etc.
It is still a further object of the invention to provide a system for purification of aqueous solutions, which comprises:
(i) an electrolysis cell comprising at least one anode and at least one cathode as electrodes positioned in an electrolyzer zone. The electrodes are spaced sufficiently close to one another to provide an interelectrode gap capable of minimizing cell voltage and IR loss. Also included is a conduit means for directly feeding a contaminated aqueous electrolyte solution to the electrodes in the electrolyzer zone. The electrolysis cell is characterized by an open configuration.
(ii) A control valve means for regulating the flow of contaminated aqueous-electrolyte solution to the electrodes directly via the conduit means of (i) above.
(iii) Means are included for pumping contaminated aqueous electrolyte solution through the conduit means, and then
(iv) rectifier means are included for providing a DC power supply to the electrolysis cell.
The purification system may also include sensor means and computerized means for receiving input from the sensor means and providing output for controlling at least one operating condition of the system selected from the group consisting of current density, flow rate of contaminated aqueous solution to the electrolysis cell, temperature and pH of the contaminated aqueous electrolyte solution. Optional components include exhaust means for further handling of electrochemically produced gaseous by-products; means for pretreatment of the contaminated aqueous electrolyte solution selected from the group consisting of filtration, pH adjustment and temperature adjustment.
As previously discussed, the electrochemical cells of this invention are especially novel in their “open configuration.” As appearing in the specification and claims, the expression “open configuration” or variations thereof are defined as electrochemical cell designs adapted for controlled leakage or discharge of treated and decontaminated aqueous electrolyte solution and gaseous or volatile by-products. The above definition is also intended to mean the elimination or exclusion of conventional closed electrochemical cells and tank type cell designs utilizing conventional indirect means for feeding electrolyte to electrodes. Closed flow type electrochemical cells, for example, are often fabricated from a plurality of machined and injection molded cell frames which are typically joined together under pressure into a non-leaking sealed stack with gaskets and O-rings to avoid any leakage of electrolyte from the cell. This type of sealed electrochemical cell is typically found in closed plate and frame type cells. Very close fitting tolerances for cell components are required in order to seal the cell and avoid leakage of electrolyte and gases to the atmosphere. Consequently, initial capital costs of such electrochemical cells, refurbishment costs, including replacement costs for damaged cell frames and gasketing from disassembly of closed plate and frame type cells are high.
Because the configuration of the electrochemical cells of this invention is “open”, and not sealed, allowing for controlled leakage of aqueous electrolyte solution and gaseous by-products, sealed cell designs, including gaskets, O-rings and other sealing devices are eliminated. Instead, cell component parts are retained together in close proximity by various mechanical means when needed, including, for instance, clamps, bolts, ties, straps, or fittings which interact by snapping together, and so on. As a result, with the novel open cell concept of this invention initial cell costs, renewal and maintenance costs are minimized.
In the open configuration cells of this invention, electrolyte is fed directly to the electrodes in the electrolyzer zone from a feeder which may be positioned centrally relative to the face of the electrodes, for example, where the contaminated solution engages with the electrodes by flowing through very narrow interelectrode gaps or spaces between the electrodes. During this period the contaminants in the aqueous solution are either directly converted at the electrodes to less hazardous substances and/or through the autogenous generation of chemical oxidants or reductants, such as chlorine, bleach, i.e., hypochlorite; hydrogen, oxygen, or reactive oxygen species, like ozone, peroxide, e.g., hydrogen peroxide, hydroxy radicals, and so on, chemically modified to substances of lesser toxicity, like carbon dioxide, sulfate, hydrogen, oxygen and nitrogen. In some instances, depending on the compositional make-up of pollutants in the solution being treated, it may be desirable to add certain salts like sodium chloride at low concentration to the solution before treatment in the cell. For example, this could be used to generate some active chlorine to provide a residual level of sterilant in the treated water. Likewise, oxygen or air may be introduced into the feed stream to enhance peroxide generation.
Because electrolyte is fed directly to the electrode stack usually under positive pressure, gases such as hydrogen and oxygen generated during electrolysis are less prone to accumulate over electrode surfaces by forming insulative blankets or pockets of bubbles. Gas blinding of electrodes produces greater internal resistance to the flow of electricity resulting in higher cell voltages and greater power consumption. However, with direct flow of electrolyte to the cell, the dynamic flow of solution in interelectrode gaps, according to this invention, minimizes gas blanketing, and therefore, minimizes cell voltages.
The aqueous solution entering the cell by means of pumping or gravity feed, cascades over and through available interelectrode gaps, and on exiting the electrolyzer zone of the cell through gravitational forces, descends downwardly into a reservoir, for post treatment, for example, or discharged, such as into a natural waterway. Any undissolved gases generated by electrolysis, in contrast, are vented upwardly from the cell to the atmosphere or may be drawn into a fume collector or hood, if necessary, for collection or further processing.
While the direct feed “open configuration” electrochemical cells, as described herein, preferably provide for the elimination of conventional cell housings or tanks, as will be described in greater detail below, the expression “open configuration” as appearing in the specification and claims, in addition to the foregoing definition, is also intended to include electrochemical cell designs wherein the directly fed electrodes are disposed in the interior region of an open tank or open cell housing. A representative example of an open tank electrochemical cell is that disclosed by U.S. Pat. No. 4,179,347 (Krause et al) used in a continuous system for disinfecting wastewater streams. The cell tank has an open top, a bottom wall, sidewalls and spaced electrodes positioned in the tank interior. Instead of feeding the contaminated aqueous solution directly to the electrodes positioned in the tank the electrolyte, according to Krause et al, is initially fed to a first end of the tank where interior baffles generate currents in the wastewater causing it to circulate upwardly and downwardly through and between the parallel electrodes. Hence, instead of delivering electrolyte directly to the electrode stack where under pressure it is forced through interelectrode gaps between adjacent anodes and cathodes according to the present invention, the electrolyte in the open tank cell of Krause et al indirectly engages with the electrodes through a flooding effect by virtue of the positioning of the electrodes in the lower region of the tank where the aqueous solution resides. This passive, flooding effect is insufficient to achieve the mass transport conditions necessary for efficient destruction particularly of contaminants when present in low concentrations. Consequently, gaseous by-products of the electrolysis reaction can and often do result in the development of a blanket of gas bubbles on electrode surfaces. This generates elevated cell voltages and greater power consumption due to higher internal resistances.
Accordingly, for purposes of this invention the expression “open configuration” as appearing in the specification and claims is also intended to include open tank type electrochemical cells wherein the electrode stack is positioned in the interior of an open tank/housing and includes means for directly feeding contaminated aqueous solutions to the electrodes. With direct feeding the housing does not serve as a reservoir for the contaminated aqueous solution which otherwise would passively engage the electrodes indirectly by a flooding effect.
For purposes of this invention, it is to be understood the expression “open configuration” is also intended to allow for safety devices positioned adjacent to the electrochemical cells and purification systems, such as splash guards, shields and cages installed for minimizing the potential for injuries to operators. Hence, the confinement of the electrolysis cells or an entire water purification system of this invention inside a small room, for example, is also intended to be within the meaning of “open configuration” as appearing in the specification and claims.
A further type of electrochemical cell design is disclosed by Beck et al in U.S. Pat. No. 4,048,047. The Beck et al cell design comprises a bipolar stack of circular electrode plates separated by spacers to provide interelectrode gaps ranging from 0.05 to 2.0 mm. Liquid electrolyte is fed directly to the electrode plates through a pipeline into a central opening in the electrode stack and then outwardly so it runs down the outside of the stack. However, the electrode stack is placed in a conjoint closed housing with a covering hood to avoid loss of gaseous reactants, vapors or reaction products. Thus, the closed configuration of the Beck et al cell does not meet the criteria of an “open configuration” cell according to this invention.
While it has been pointed out the “open configuration” of the improved, highly economic electrochemical cell designs of this invention are based on the elimination of traditional closed cell designs, including plate and frame type cells and conventional tank type cells, as well as traditional partially open tank type cell designs, whether batch or continuous, it is to be understood, the expression “open configuration”, as appearing in the specification and claims, also contemplates electrochemical cells which may be modified with various inserts, barriers, partitions, baffles, and the like, in some instances positioned adjacent to cell electrodes, or their peripheral edges. Such modifications can have the effect of altering electrolyte circulation and direction, and increase residency/retention time, and therefore, affect the residency time and rate of discharge of electrolyte from the cell. Notwithstanding, such modified electrochemical cells which are made partially open fall within the intended meaning of “open configuration” when the electrodes per se remain substantially accessible. Representative modified electrochemical cell designs with electrodes which remain substantially accessible that are included within the definition for “open configuration” as appearing in the claims include modified, so called “Swiss roll cell” designs wherein, for example, the closed tubular containment for the electrodes, which are superimposed onto one another and rolled up concentrically, is removed, thereby forming an “open type Swiss roll cell”.
It is yet a further object of the invention to provide a more efficient electrochemical cell design which can be used in effectively treating a wide spectrum of both chemical and biological contaminants in aqueous media, but also of varying concentration (from less than a few ppm to several thousand ppm) which is both economically competitive in capital costs and power consumption to more conventional water purification systems. The electrochemical systems and methods of the invention have such significantly improved economics, as to be readily adaptable to treating via continuous processes, large volumes of industrial waste waters from manufacturing facilities, such as chemical plants, textile plants, paper mills, food processing plants, and so on. Lower cell voltages and higher current densities are achieved with the highly economic, open configuration, especially when configured as monopolar electrochemical cells equipped with electrodes having narrow capillary interelectrode gaps. Generally, the width of the gap between electrodes is sufficiently narrow to achieve conductivity without extra supporting electrolytes or current carriers being added to the contaminated aqueous solutions. Thus, the need for adding supporting electrolyte to the contaminated aqueous electrolyte solution as supporting current carrier can be avoided. Because of the open configuration, as defined herein, the electrochemical cells of this invention can be readily configured to a monopolar design. This is especially advantageous since higher current densities would be desirable ih electrolyzing contaminated aqueous solutions having relatively low conductivities while still also maintaining low cell voltages. Likewise, the improved electrochemical cells of this invention may have a bipolar configuration, especially for large installations to minimize busbar and rectifier costs.
It is thus a further object of the invention to provide for improved, more economic and safer continuous, semi-continuous or batch methods for electropurification of contaminated aqueous solutions by the steps of:
(i) providing an electrolysis cell comprising at least one anode and at least one cathode as electrodes positioned in an electrolyzer zone. The electrodes are spaced sufficiently close to one another to provide an interelectrode gap capable of minimizing cell voltage and IR loss. Means are provided for direct feeding a contaminated aqueous solution to the electrodes in the electrolyzer zone. Means are provided for regulating the residency time of the electrolyte solution in the electrolyzer zone during electrolysis for modification of the contaminants. The electrolysis cell is characterized by “open configuration” as previously described;
(ii) directly feeding into the electrolyzer zone of the electrolysis cell a contaminated aqueous electrolyte solution, and
(iii) imposing a voltage across the electrodes of the electrolysis cell to modify, and preferably destroy the contaminants in the aqueous electrolyte solution.
It will be understood that generally the process will include the step of recovering a purified electrolyte solution from the electrolysis cell. However, the invention contemplates direct delivery of purified aqueous solutions to a watershed, for example, or optionally to other post-treatment stations.
As previously mentioned, the methods is performed in an open configuration electrolysis cell which may be either monopolar or bipolar configuration.
For a further understanding of the invention and its characterizing features reference should now be made to the accompanying drawings wherein:
FIG. 1 is a side elevational view illustrating a first embodiment of a direct feed, open configuration, controlled leakage electrochemical cell of the invention wherein the electrodes are positioned above a water collection vessel in a horizontal orientation;
FIG. 2 is a side elevational view of the electrochemical cell of FIG. 1 except the electrodes are in a vertical orientation;
FIG. 3 is a side elevational view illustrating a second embodiment of a direct feed, open configuration, controlled leakage electrochemical cell of the invention wherein the electrodes are positioned in the interior of an open cell housing;
FIG. 4 is an exploded view of the electrode cell stack of FIG. 1.
FIG. 5 is a side elevational view of an electrode stack of the invention connected in a monopolar configuration;
FIG. 6 is a side elevational view of an electrode stack of the invention connected in a bipolar configuration;
FIG. 7 is an elevational view of an electrode stack compartmentalized with a separator, and
FIG. 8 illustrates the results of electropurification of an aqueous solution of phenol decontaminated according to the methods of the invention, as performed in Example I
Turning first to FIG. 1 there is illustrated an electrochemical cell 10 for purification of contaminated aqueous solutions, as previously discussed, represented by contaminated water 12 passing through inlet 22. The contaminated water 12 is treated in the electrolyzer zone 14 of cell 10 which is illustrated in a fully open configuration allowing gaseous by-products of the electrolysis reaction, such as oxygen and hydrogen 16 to be released to the atmosphere. It may be desirable in some instances to collect certain potentially hazardous gases generated during the electrolysis reaction to avoid discharging to the atmosphere. Chlorine, for example, may be generated at the anode during electrolysis of aqueous effluent streams containing brine or sea water. Such gases can be recovered, for instance, by a vacuum powered hood device of conventional design (not shown) positioned adjacent to electrochemical cell 10.
The electrolyzer zone 14 includes an electrode stack 17 shown in a horizontal orientation in FIGS. 1 and 4, and comprises at least one cathode 18 and at least one anode 20. Anodes 20, for example, may also serve as end plates 21 for holding an assembly of electrodes, spacers, and separators, whenever used, into an assembled electrode stack 17. Non-conductive electrode spacers 23 positioned between electrodes provide the desired interelectrode gap or spacing between adjacent anodes and cathodes. While FIGS. 1 & 4 of the drawings may be shown with only a central cathode with anodes on opposite sides of cathode 18, for example, it is to be understood the electrode stacks may be formed from several alternating anodes, spacers, cathodes, and so on, with bolting means 25 running through the stack and end plates for maintaining the components in a structurally stable assembly.
The end plates, electrodes and spacers may have a generally rectangular geometry. However, any number of possible alternative geometrical shapes and sizes are within the purview of the invention, including square, round or circular configurations, to name but a few. Contaminated aqueous electrolyte solutions are fed directly to the electrodes in electrolyzer zone 14 via supply line 22. Supply line 22 is shown centrally positioned relative to anode/end plate 21. The electrodes, which may be solid and planar, are preferably mesh/screen-type materials. This enables the aqueous electrolyte solutions entering the electrode stack to directly engage with the electrodes, and in so doing flow radially across the face of the individual electrode surfaces within the stack toward their peripheral edges. In addition, the entering solution usually flows axially, or normal to the longitudinal axis of the plane of the electrodes, so the contaminated aqueous solution simultaneously cascades over and through the electrode stack in a fountain-like effect to maximize contact with electrode surfaces in the process. Purified water 24, free or virtually free of contaminants exiting electrolyzer zone 14, can be collected in an open tank 26, or funneled into a discharge line (not shown) for emptying into a natural watershed, etc.
It will be understood the direct feed of contaminated aqueous solutions to the electrolyzer zone need not be centrally positioned relative to the electrode stack, as illustrated in FIGS. 1-4. Alternative direct feed routes include inverting the point of feed, so that contaminated aqueous solutions are fed from the bottom of the electrode stack, or at an oblique or obtuse angle to the planar surface of the electrodes. In addition, the direct feed entry point may also be axial with the edge of the planar surface of the electrodes wherein contaminated solution is delivered to the peripheral edge of an electrode stack.
A convenient means for regulating the residency time of the contaminated aqueous solution in electrolyzer zone 14 and for controlling leakage of decontaminated and purified water 24 therefrom can be through valve 28 and/or pumping means of conventional design (not shown). The flow rate of contaminated water directly entering the electrode stack and exiting the stack as decontaminated water can be regulated through manual or automated flow control valve 28 of standard design. The flow rate (liters/minute)is adjusted, so it is sufficient to provide effective destruction of pollutants by the time the treated solution exits the electrolyzer zone. Persons of ordinary skill in the art having the benefit of this disclosure will also recognize the performance of the electrochemical cells of this invention may be optimized by alternative means, such as increasing the path of the solution in the electrolyzer zone. The installation of baffles, for instance, can increase the dwell time of the solution in the electrolyzer zone. Alternative means include enlarging the surface area of the electrodes for reducing the residency time in the electrolysis zone. In practice, electrochemists skilled in the art will also recognize the performance of the cell can be increased with higher current densities.
Because of cell geometry, and the ability to conveniently use both monopolar and bipolar configurations, practically any electrode material can be employed, including metals in the form of flat sheet, mesh; foam or other materials, such as graphite, vitreous carbon, reticulated vitreous carbon and particulate carbons. This also includes combinations of electrode materials, such as bilayer structures comprising two metal layers separated by appropriate insulating or conductive materials, and so on.
Representative examples of useful anodes would include those generally known as, noble metal anodes, dimensionally stable anodes, carbon, vitreous carbon and graphite-containing anodes, doped diamond anodes, substoichiometric titanium oxide-containing anodes and lead oxide-containing anodes. More specific representative examples include platinized titanium noble metal anodes; anodes available under the trademark DSA-O2, and other anodes, such as high surface area type anodes like felts, foams, screens, and the like available from The Electrosynthesis Co, Inc., Lancaster, N.Y. Other anode materials comprise ruthenium oxide on titanium, platinum/iridium on titanium, iridium oxide on titanium, silver oxide on silver metal, tin oxide on titanium, nickel III oxide on nickel, gold, substoichiometric titanium oxides, and particularly the so called Magneli phase titanium oxides having the formula TiOx wherein x ranges from about 1.67 to about 1.9. A preferred specie of substoichiometric titanium oxide is Ti4O7. Magneli phase titanium oxides and methods of manufacture are described in U.S. Pat. No. 4,422,917 (Hayfield) which teachings are incorporated-by-reference herein. They are also commercially available under the trademark Ebonex®. Where electrocatalytic metal oxides, like PbO2, RuO2, IrO2, SnO2, Ag2O, Ti4O7 and others are used as anodes, doping such oxides with various cations or anions has been found to further increase the electrocatalytic oxidation behavior, stability, or conductivity of the decontamination reactions of this invention. The selection of appropriate anode materials is made by considering such factors as cost, stability of the anode material in the solutions being treated and its electrocatalytic properties for achieving high efficiencies.
Suitable cathode materials include metals, such as lead, silver, steel, nickel, copper, platinum, zinc, tin, etc., as well as carbon, graphite, Ebonex, various alloys, and so on. Gas diffusion electrodes are also useful in the methods of this invention. In this regard, they may be used as cathodes in converting oxygen or air to useful amounts of peroxide, minimizing hydrogen evolution and/or for lowering cell voltages. The electrode material, whether anode or cathode, may be coated with an electrocatalyst, either low or high surface area. Higher surface area electrodes, for example, expanded metal screens, metal or graphite beads, carbon felts, or reticulated vitreous carbon are especially useful in achieving higher efficiencies for destruction of toxic or hazardous substances when present at low concentrations in the aqueous electrolyte.
Specific anode and cathode materials are selected on the basis of cost, stability and electrocatalytic properties. For example, persons of ordinary skill in the art of electrochemistry will recognize which electrode material to select when it is desired to convert chloride to chlorine; water to ozone, hydroxyl radicals or other reactive oxygen species; oxygen or air to hydrogen peroxide or hydroxyl radicals via electrochemically generated Fenton's reagent using for instance, a slowly dissolving iron-containing_metal anode; and catalytic reduction of nitrate to nitrogen or of_organohalogen compounds to halide ions and organic moieties of lesser toxicity.
Of special importance in the selection of electrocatalytic anode and cathode materials occurs when treating aqueous solutions comprising complex mixtures of pollutants wherein electrode materials may be selected for paired destruction of pollutants. For example, an aqueous stream contaminated with organics, microorganisms and nitrate pollutants may be treated simultaneously in the same electrochemical cell using paired destruction methods with a reactive oxygen species generating anode, such as platinum on niobium or Ebonex for destruction of microorganism and oxidation of organics. In addition, the same. cell could also be equipped with a lead cathode for nitrate destruction.
As previously mentioned, non-conductive electrode spacers 23 provide the desired interelectrode gap or spacing between adjacent anodes and cathodes. The thickness of spacers 23, which are non-conductive, insulative porous mesh screens fabricated from polymeric materials, such as polyolefins, like polypropylene and polyethylene, determines the width of the interelectrode gap. Alternatively, it is permissible to employ ionic polymer spacers which can effectively increase the ionic conductivity of the cell, so as to reduce cell voltage and operating costs further. Ion-exchange resins of suitable dimensions, like cation and anion exchange resin beads are held immobile within the gap between electrodes.
For most applications, the interelectrode gap ranges from near zero gap, to avoid electrode shorting, to about 2 mm. More specifically, this very small capillary size gap is preferably less than a millimeter, ranging from 0.1 to <1.0 mm. The very small interelectrode gap makes possible the passage of current through relatively non-conductive media. This is the case, for example, in water contaminated with organic compounds. Thus, with the present invention it is now possible to destroy contaminants in solution without adding any current carrying inorganic salts to increase the ionic conductivity of the aqueous media. Furthermore, the very narrow interelectrode gap provides the important advantage of lower cell voltages which translates into reduced power consumption and lower operating costs. Hence, the combination of open configuration electrochemical cells and very narrow interelectrode gaps of this invention provide for both lower initial capital costs, as well as lower operating costs. This achievement is especially important in large volume applications, as in the purification of drinking water, and wastewater, according to the claimed processes.
FIG. 2 represents a further embodiment of the electrochemical cells of this invention wherein the electrolyzer zone 30 is also in an open configuration. The electrolyte 32 is fed directly to the electrode stack 34 which is in a vertical orientation. As a result, treated aqueous solution 36 is shown exiting mainly from both the top and bottom peripheral edges of electrode stack 34. This may be altered further depending on the use of baffles, for instance, in controlling residency time for the solution being treated. Purified solution is collected in vessel 38 below electrolyzer zone 30.
FIG. 3 represents still a: third embodiment of the invention wherein the electrolyzer zone 40 comprises an electrode stack 42, as discussed above, positioned in the interior of an open housing/tank 44. Housing 44 is open at the top allowing gaseous by-products of the electrolysis reaction, like hydrogen and oxygen, for instance, to be readily discharged into the atmosphere or collected through aid of an appropriate device, such as a hood (not shown). Aqueous contaminated electrolyte solution 46 is fed directly to electrode stack 42 positioned in open housing 44, unlike other tank cells wherein the electrodes receive solution indirectly as a result of their immersion in the solution delivered to the tank. Purified water 48 cascading downwardly as a result of gravitational forces collects at the bottom of the interior of housing 44, and is withdrawn.
An important advantage of the open configuration electrochemical cells of this invention resides in their ability to be readily adaptable to either a monopolar or bipolar configuration. In this regard, FIG. 5 illustrates a monopolar open configuration electrochemical cell. In the monopolar cell of FIG. 5, anodes 52, 54 and 56 each require an electrical connector as a current supply, in this case through a bus 58 as a common “external” supply line similarly, cathodes 60 and 62 each require an electrical connection shown through a common bus 64. It is also characteristic of the monopolar cell design that both faces of each electrode are active, with the same polarity.
Because water purification for a municipality, in general, is a large volume application, lowest possible cell voltages are essential in order to minimize power consumption. The open configuration, monopolar cell design of the present invention in combination with very narrow interelectrode gaps offers not only the benefits of lower initial capital costs, but also low operating costs, due to lower internal resistances, lower cell voltages and higher current densities. This combination is especially desirable when treating contaminated aqueous media of relatively low conductivity without the addition of inorganic salts as current carriers in accordance with certain embodiments of this invention, e.g., aqueous solutions contaminated with non-polar, organic solvents.
The open configuration, monopolar, controlled leakage electrochemical cells with very narrow interelectrode gaps of this invention are particularly unique in light of the Beck et al cells of U.S. Pat. No. 4,048,047. The closed configuration of the electrochemical cells of Beck et al make it very difficult and costly to achieve a monopolar connection with high current densities associated with external electrical contacts to each electrode. By contrast, with the open configuration of the electrochemical cells of this invention electrical connections to individual electrodes are facilitated, irrespective of whether the cell is a monopolar or bipolar design. Thus, the closed, bipolar electrochemical cell configuration of Beck et al would not be economic and cost competitive with the improved electrochemical cells of the present invention, or with other non-electrochemical technologies used in high volume water purification processes.
As previously indicated, the open configuration, controlled leakage electrochemical cells of this invention having very narrow capillary interelectrode gaps are also readily adaptable to bipolar configuration. FIG. 6 illustrates open configuration bipolar cell 70, according to the present invention, requiring only two “external” electrical contacts 72 and 74 through two end electrodes/end plates 76 and 78. Each of inner electrodes 80, 82 and 84 of the bipolar cell has a different polarity on opposite sides. While the bipolar cell can be quite economic in effectively utilizing the same current in each cell of the electrode stack, one important aspect of the invention relates to treating solutions by passing a current through relatively non-conductive media using very narrow interelectrode gaps. That is, the contaminated aqueous solutions can have relatively low conductivities, about equivalent to that of tap water. In order to efficiently treat such solutions it would be desirable to operate at higher current densities. The monopolar cell configurations of the invention enable operating at desired low cell voltages and high current density. While not specifically illustrated, it will be understood standard power supplies are utilized in the electrolysis cells of the invention, including DC power supply, AC power supply, pulsed power supply and battery power supply.
The invention also contemplates open configuration electrochemical cells with distributor means for contaminated aqueous electrolyte solutions, such as a length of pipe 81 with multiple openings or pores, or a feeder tube extending from the contaminated aqueous electrolyte feed inlet through the depth of the electrode stack in the electrolyzer zone. This can provide more uniform flow of solution to the electrode elements. Especially useful for stacks containing many electrode elements, these porous tubes of metal or plastic material, of sufficient porosity, diameter and length, are applicable to monopolar, bipolar, and for example, Swiss roll cells of open configuration. For deep cell stacks with electrode elements, each of larger surface area, more than one porous feeder tube may be provided, manifolded together with the feed inlet conduit.
The open configuration, bipolar type, controlled leakage electrochemical cells of the present invention can be most effectively used in the purification of aqueous solutions possessing greater ionic conductivities than those previously discussed, allowing for economical operation at lower current densities. In each instance, the open configuration of the electrochemical cells of this invention facilitates their electrical connection, whether the cell is a monopolar or bipolar design.
Most desirably, large volume applications like water purification require low capital and operating costs in order to be economically attractive. These inventors found that capital costs are largely reduced by eliminating the need for precision machined components, gasketing, costly membranes and cell separators. Lower operating costs can be achieved through lower cell voltages from narrow interelectrode gaps and lower IR from elimination of cell membranes and separators, i.e., undivided electrochemical cells. The smaller interelectrode gap, however, also makes possible the operation of the cells of this invention in an organic media, for example, containing low concentrations of supporting electrolyte, with a variety of electrode, insulator materials, and so on. Many of such applications would be readily adaptable to the open cell configuration of this invention, but with use of a cell divider forming anolyte and catholyte compartments, such as membranes or cell separators. Examples of useful processes for the electrochemical cells of this invention would include mediated reactions in electrochemical synthesis in which the objective of the membrane or separator would be to prevent reduction of anodically produced species at the cathode, and/or oxidation of cathodically produced species at the anode.
FIG. 7 is a representative example of an open configuration electrochemical 90 having anode/end plates 92 and 94 with central cathode 96 and cation exchange membranes 98 and 100 positioned between the electrodes. Membranes 98 and 100 prevent mixing of the anolyte and catholyte in the cell while the solution is allowed to flow through opening 102 in the center of the membrane.
Those embodiments of the electrochemical cells employing a diaphragm or separator are preferably equipped with ion-exchange membranes, although porous diaphragm type separators can be used. A broad range of inert materials are commercially available based on microporous thin films of polyethylene, polypropylene, polyvinylidene-difluoride, polyvinyl chloride, polytetrafluoro-ethylene (PTFE), polymer-asbestos blends and so on, are useful as porous diaphragms or separators.
Useful cationic and anionic type permselective membranes are commercially available from many manufacturers and suppliers, including such companies as RAI Research Corp., Hauppauge, N.Y., under the trademark Raipore; E.I. DuPont, Tokuyama Soda, Asahi Glass, and others. Generally, those membranes which are fluorinated are most preferred because of their overall stability. An especially useful class of permselective ion exchange membranes are the perfluorosulfonic acid membranes, such as those available from E.I. DuPont under the Nafion® trademark. The present invention also contemplates membranes and electrodes formed into solid polymer electrolyte composites. That is, at least one of the electrodes, either anode or cathode or both anode and cathode, are bonded to the ion exchange membrane forming an integral component.
In the purification of solutions the invention provides for the treatment of low conductivity media. However, it may be necessary to add very low concentrations of inert, soluble salts, such as alkali metal salts, e.g. sodium or potassium sulfate, chloride, phosphate, to name but a few. Stable quaternary ammonium salts may also be employed. As previously mentioned, ion exchange resin beads of appropriate size can be inserted in the spaces between the electrodes to increase conductivity. This will provide further reductions in cell voltage and total operating costs.
Contaminated solutions entering the cell can range in temperature from near freezing to about boiling, and more specifically from about 40° to about 90° C. Higher temperatures can be beneficial in lowering cell voltages and increase rates of contaminant destruction. Such higher temperatures can be achieved, if needed, by preheating the incoming solution, or through IR heating in the cell, especially when solution conductivities are low, as for example in purification of drinking water. By suitably adjusting the cell voltage and residence time in the cell, beneficial temperatures in the above ranges are possible.
As a preferred embodiment of the invention, as an undivided cell, for the purification of contaminated aqueous solutions a variety of useful anode and cathode species can be generated during electrolysis which in turn aid in the chemical destruction of contaminants and the purification of the aqueous solutions. They include such species as oxygen, ozone, hydrogen peroxide, hydroxyl radical, and other reactive oxygen species. Less preferred species, although useful in the process include the generation of chlorine or hypochlorite (bleach) through the electrolysis of brine or sea water. While not wishing to be held to any specific mechanism of action for the success of the processes in the decontamination, decolorization and sterilization of aqueous solutions contaminated with toxic organics and microorganisms, several processes, including those previously mentioned, may be occurring simultaneously. They include, but are not limited to the direct oxidation of contaminants at the anode; destruction of contaminants by direct reduction at the cathode; oxygenation of the feed stream by micro bubbles of oxygen produced at the anode; degasification of volatiles in the feed stream by oxygen and hydrogen micro bubbles; IR heating in the cell; aeration of the water stream exiting the open cell, and so on.
A broad range of compounds, microorganisms and other hazardous substances as previously discussed are successfully destroyed in the open cell configuration of the invention employing the processes as described herein. Representative examples include aliphatic alcohols, phenols, nitrated or halogenated aromatic compounds, and so on. Color reduction or complete elimination of color can also be achieved, along with disinfection, including the destruction of viruses.
The following specific examples demonstrate the various embodiments of the invention, however, it is to be understood they are for illustrative purposes only and do not purport to be wholly definitive as to conditions and scope.
A monopolar electrochemical cell having an open configuration was set up with an electrode stack comprising 316 stainless steel end plates each with a diameter of 12.065 centimeters and a thickness of 0.95 centimeters. The end plates were connected as cathodes. A central cathode was also assembled into the stack and consisted of 316 stainless steel mesh with 7.8×7.8 openings/linear centimeter, 0.046 centimeter wire diameter, 0.081 centimeter opening width and 41 percent open area. The anodes consisted of two platinum clad niobium electrodes manufactured by Blake Vincent Metals Corp. of Rhode Island. The anodes which were clad on both sides of the niobium substrate had a thickness of 635 micrometers, were expanded into a mesh with a thickness of about 0.051 centimeters, with 0.159 centimeter diamond shaped interstices. The spacers positioned between adjacent electrodes were fabricated from polypropylene mesh with 8.27×8.27 openings/linear centimeter, 0.0398 centimeter thread diameter, 0.084 centimeter opening and a 46 percent open area was supplied by McMaster-Carr of Cleveland, Ohio. The gap between the electrodes was approximately 0.04 centimeters, determined by the thickness of the polypropylene mesh. A schematic of the electrochemical cell corresponds to FIG. 1 of the drawings, except a hood was omitted. Recirculation of the aqueous solution between the glass collection tank and the cell was effected by means of an AC-3C-MD March centrifugal pump at a flow rate of about 1 liter/minute. A Sorensen DCR 60-45B power supply was used to generate the necessary voltage drop across the cell.
A test solution was prepared containing 1 g of phenol in 1 liter of tap water. The solution was recirculated through the cell while a constant current of 25 amps was passed. The solution which was initially clear turned red after about 2-3 minutes into the treatment process, possibly indicating the presence of quinone-type intermediates. The initial cell voltage of 35 V decreased rapidly to 8-9 V, and the temperature of the solution stabilized at about 56-58° C. Samples taken were analyzed periodically for total organic carbon (TOC). The results, which are shown in FIG. 8, appear to suggest the decrease in TOC is from the phenol probably undergoing complete oxidation to carbon dioxide which is then eliminated as gas from the solution.
In order to demonstrate color reduction in a textile effluent 1 liter of solution was prepared with tap water containing 0.1 g of the textile dye Remazol™ Black B (Hoechst Celanese), 0.1 g of the surfactant Tergitol™ 15-S-5 (Union Carbide) and 1 g of NaCl.
The composition of the test solution was similar to that of typical effluents produced in textile dyeing processes where even very low concentrations of Remazol Black impart very strong coloration to solutions. Remazol Black is a particularly difficult to treat textile dye. Heretofore, other methods used to treat Remazol Black, such as by ozonation or with hypochlorite bleach have failed to produce satisfactory color reduction.
The above solution containing Remazol Black was electrolyzed in the monopolar cell set up of Example I above, at a constant current of 25 amps. The cell voltage was about 25 V, and the temperature of the solution reached 52° C. The initial color of the solution was dark blue. After 10 minutes of electrolysis the color of the solution turned to pink, and after 30 minutes the solution was virtually colorless.
A further experiment was conducted in order to demonstrate the decontamination of ground water. Humic acids are typical contaminants of ground water, produced by the decomposition of vegetable matter. Water containing humic acids is strongly colored even at low concentrations, and the elimination of the color can be difficult.
A dark brown solution in tap water was prepared containing 30 ppm of the sodium salt of humic acid (Aldrich) without any additives to increase the electrical conductivity of the solution. The solution was recirculated through a monopolar electrochemical cell similar to that used in Example I, but equipped with only one anode and two cathodes. A constant current of 10 amps was passed for 2.5 hours. The cell voltage was 24-25 volts, and the temperature reached 58° C. At the end of the experiment the solution was completely clear, demonstrating the effective destruction of humic acid.
A further experiment was conducted to demonstrate the effectiveness of the electrolysis cells and methods of this invention in the sterilization and chemical oxygen demand (COD) reduction in effluents from food processing plants.
250 ml of wastewater from a Mexican malt manufacturing company was treated using a monopolar, open electrochemical cell similar to that employed in Example I, except the total anode area of 6 cm2. The objectives were to reduce the COD, partial or total reduction of the color, elimination of microorganisms and odor.
A current of 1 amp was passed for 150 minutes; the initial cell voltage of 22 V dropped to 17.5 V, and the temperature of the solution reached 44° C.
The results are shown in the following Table:
A further experiment was conducted to demonstrate the effectiveness of the electrolysis cells and methods of this invention in the removal of color in a single-pass configuration.
A dark purple solution containing methyl violet dye in tap water at a concentration of 15 ppm was circulated through a monopolar, open electrochemical cell similar to that employed in Example 1, in single-pass mode, at a flow rate of 250 ml/minute. The objective was to achieve total reduction of the color.
A current of 25 amp was passed; the cell voltage was 25 V, and the temperature of the solution reached 65° C.
After a single pass through the cell a clear solution was obtained.
An experiment can be conducted to demonstrate the utility of the open configuration electrochemical cell in the electrosynthesis of chemicals, in this instance sodium hypochlorite.
The electrochemical cell of Example I is modified by replacing the anodes with catalytic chlorine evolving anodes, such as DSA® anodes manufactured by Eltech Systems. A solution of brine containing 10 g of sodium chloride per liter is introduced into the electrolyzer zone wherein chlorine is generated at the anode and sodium hydroxide is produced at the cathode. The chlorine and caustic soda are allowed to react in the cell to produce a dilute aqueous solution of sodium hypochlorite bleach.
While the invention has been described in conjunction with various embodiments, they are illustrative only. Accordingly, many alternatives, modifications and variations will be apparent to persons skilled in the art in light of the foregoing going detailed description, and it is therefore intended to embrace all such alternatives and variations as to fall within the spirit and broad scope of the appended claims.
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3793173||Feb 3, 1969||Feb 19, 1974||M Kawahata||Wastewater treatment using electrolysis with activated carbon cathode|
|US3859195 *||Oct 17, 1973||Jan 7, 1975||Du Pont||Apparatus for electrochemical processing|
|US3919062||Apr 29, 1974||Nov 11, 1975||Grace W R & Co||Electrochemical system graduated porous bed sections|
|US3923629||Mar 25, 1974||Dec 2, 1975||Carborundum Co||Electrolytic cell for inactivation and destruction of pathogenic material|
|US3926771||Oct 3, 1974||Dec 16, 1975||Diamond Shamrock Corp||Apparatus for electrosanitizing waste water|
|US4040938||Mar 18, 1975||Aug 9, 1977||Peter Murday Robertson||Electrode arrangement for electrochemical cells|
|US4048047||Jan 14, 1976||Sep 13, 1977||Basf Aktiengesellschaft||Electrochemical cell with bipolar electrodes|
|US4061556||Mar 10, 1977||Dec 6, 1977||Sachs-Systemtechnik Gmbh||Portable electrolytic apparatus for purifying drinking water|
|US4062754||Aug 27, 1975||Dec 13, 1977||Sachs Systemtechnik Gmbh||Apparatus for destroying microorganisms in an aqueous liquid by electrolytic oxidation|
|US4085028||Nov 21, 1974||Apr 18, 1978||Electro-Chlor Corporation||Electrolytic chlorination device|
|US4100052||Nov 11, 1976||Jul 11, 1978||Diamond Shamrock Corporation||Electrolytic generation of halogen biocides|
|US4179347||Feb 28, 1978||Dec 18, 1979||Omnipure, Inc.||System for electrocatalytic treatment of waste water streams|
|US4326941||Jun 23, 1980||Apr 27, 1982||Kemanord Ab||Electrolytic cell|
|US4406768||Dec 24, 1981||Sep 27, 1983||Monsanto Company||Electrochemical cell assembly|
|US4445990||Nov 12, 1981||May 1, 1984||General Electric Company||Electrolytic reactor for cleaning wastewater|
|US4500403||Jul 8, 1983||Feb 19, 1985||Monsanto Company||Divided electrochemical cell assembly|
|US4676878||Jan 6, 1986||Jun 30, 1987||Ephriam Chez||Apparatus and method for electronic decomposition of water into aqueous free radicals and free electrons|
|US4728409||Dec 2, 1985||Mar 1, 1988||Canadian Patents And Development Limited||Perforated bipole electrochemical reactor|
|US4790923||Jul 7, 1987||Dec 13, 1988||Stillman Neil W||Liquid treating electrolytic cell|
|US4839007||Feb 17, 1988||Jun 13, 1989||Bbc Brown Boveri Ag||Method for purifying industrial waste water by direct oxidation of the organic pollutants|
|US4917782||Mar 2, 1988||Apr 17, 1990||Advanced Water Systems, Inc.||Electrolytic liquid purification process and apparatus|
|US4929359||Jan 26, 1988||May 29, 1990||The United States Of America As Represented By The United States Department Of Energy||Treatment of concentrated industrial wastewaters originating from oil shale and the like by electrolysis polyurethane foam interaction|
|US4931166||Mar 13, 1989||Jun 5, 1990||Imperial Chemical Industries Plc||Electrochemical cell|
|US4952298 *||Mar 17, 1989||Aug 28, 1990||Atochem||Corrective controller system for electrolytic cells|
|US4992156||Mar 6, 1989||Feb 12, 1991||Silveri Michael A||Electrolytic pool purifier|
|US5085753||Apr 17, 1990||Feb 4, 1992||Floatron, Inc.||Water purifier|
|US5256268||Nov 16, 1992||Oct 26, 1993||Konica Corporation||Water treatment method and apparatus|
|US5292405||Jun 17, 1992||Mar 8, 1994||Baker Hughes Incorporated||Electrolytic cell and method|
|US5364509||Jan 21, 1993||Nov 15, 1994||Eltech Systems Corporation||Wastewater treatment|
|US5395492||Jul 7, 1994||Mar 7, 1995||Schoeberl; Meinolf||Apparatus for the sterilization of water|
|US5439576||Dec 19, 1991||Aug 8, 1995||Schoeberl; Meinolf||Apparatus for the sterilization of water|
|US5549812||Mar 20, 1995||Aug 27, 1996||Wt Wassertechnologie Gmbh||Process and apparatus for processing industrial waste water by electrolysis|
|US5580438||Mar 27, 1995||Dec 3, 1996||Silveri; Michael A.||Pool purifier attaching apparatus and method|
|US5587057||Dec 7, 1993||Dec 24, 1996||David M. A. Metzler||Highly conductive liquid media electrocoagulation|
|US5647969||Jul 10, 1995||Jul 15, 1997||Motorola, Inc.||Method and system for removing ionic species from water|
|US5688387||May 4, 1994||Nov 18, 1997||Fongen; Sigurd||Turbo electrochemical system|
|US5728287||Oct 31, 1996||Mar 17, 1998||H2 O Technologies, Ltd.||Method and apparatus for generating oxygenated water|
|US5746904||Mar 5, 1996||May 5, 1998||Lee; Ming Shing||Method, apparatus and system for continuously treating water body|
|US5935412||Jun 17, 1997||Aug 10, 1999||Atlantis Limited Partnership||Method and apparatus for eliminating odors in sewage systems|
|US5954937||May 19, 1995||Sep 21, 1999||The Regents Of The University Of California||Method and apparatus for capacitive deionization and electrochemical purification and regeneration of electrodes|
|USRE37055||Dec 2, 1998||Feb 20, 2001||Michael A. Silveri||Pool purifier attaching apparatus and method|
|1||Beck, F. et al., Development of New Cells for Electro-Organic Synthesis, Chem. Ing. Tech. 41, #17, 943-950 (1969). no month.|
|2||Brinecell, Inc., 1 page, Jan. 1992.|
|3||Robertson, P. et al., A New Cell For Electrochemical Processes, J. Electroanal. Chem., 65, 883-900 (1975). no month.|
|4||Wenisch, Franz et al., Experience With An Undivided Cell, The American Institute of Chemical Engineers, No. 185, vol. 75, pp. 14-18 (1979). no month.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US6572902 *||Apr 25, 2001||Jun 3, 2003||Advanced H2O, Inc.||Process for producing improved alkaline drinking water and the product produced thereby|
|US6689262 *||Feb 21, 2003||Feb 10, 2004||Aqua Innovation, Inc.||Microbubbles of oxygen|
|US6802956 *||Jun 5, 2002||Oct 12, 2004||Aquatic Technologies||Electrolytic treatment of aqueous media|
|US6866756 *||Oct 22, 2002||Mar 15, 2005||Dennis Klein||Hydrogen generator for uses in a vehicle fuel system|
|US6869626 *||Nov 9, 2000||Mar 22, 2005||Phild Co., Ltd.||Production method of ultrafine gold particle-dissolved water and device therefor|
|US6884332||Nov 12, 2002||Apr 26, 2005||Kuntz Electroplating Inc.||Method and apparatus for treating an aqueous electroplating bath solution|
|US7011750 *||Sep 4, 2002||Mar 14, 2006||Sanyo Electric Co., Ltd.||Water treatment device|
|US7160434 *||Mar 24, 2003||Jan 9, 2007||Robert E. Moroney, Llc||Therapeutic electrolysis device|
|US7160472||Nov 19, 2003||Jan 9, 2007||Xogen Technologies Inc.||Treatment of a waste stream through production and utilization of oxyhydrogen gas|
|US7191737||Jan 18, 2005||Mar 20, 2007||Hydrogen Technology Applications, Inc.||Hydrogen generator for uses in a vehicle fuel system|
|US7332065 *||Jun 14, 2004||Feb 19, 2008||Akzo Nobel N.V.||Electrode|
|US7396441||Dec 10, 2003||Jul 8, 2008||Aqua Innovations, Inc.||Flow-through oxygenator|
|US7666317||Feb 23, 2010||MAC Aerospace Industries, Inc.||Methods and systems for disinfecting potable water supplies|
|US7670495||Mar 2, 2010||Oxygenator Water Technologies, Inc.||Flow-through oxygenator|
|US7780833||Aug 24, 2010||John Hawkins||Electrochemical ion exchange with textured membranes and cartridge|
|US7836543||Jan 19, 2007||Nov 23, 2010||Tennant Company||Method and apparatus for producing humanly-perceptable indicator of electrochemical properties of an output cleaning liquid|
|US7891046||Jan 19, 2007||Feb 22, 2011||Tennant Company||Apparatus for generating sparged, electrochemically activated liquid|
|US7959780||Jun 14, 2011||Emporia Capital Funding Llc||Textured ion exchange membranes|
|US8007654||Aug 30, 2011||Tennant Company||Electrochemically activated anolyte and catholyte liquid|
|US8012339||May 16, 2008||Sep 6, 2011||Tennant Company||Hand-held spray bottle having an electrolyzer and method therefor|
|US8012340||Jan 19, 2007||Sep 6, 2011||Tennant Company||Method for generating electrochemically activated cleaning liquid|
|US8016996||Sep 13, 2011||Tennant Company||Method of producing a sparged cleaning liquid onboard a mobile surface cleaner|
|US8025786||Jan 19, 2007||Sep 27, 2011||Tennant Company||Method of generating sparged, electrochemically activated liquid|
|US8025787||Sep 27, 2011||Tennant Company||Method and apparatus for generating, applying and neutralizing an electrochemically activated liquid|
|US8046867||Jan 19, 2007||Nov 1, 2011||Tennant Company||Mobile surface cleaner having a sparging device|
|US8062499||May 5, 2009||Nov 22, 2011||Tennant Compnay||Charge movement detector for electrochemically activated liquids|
|US8123915 *||Jun 16, 2009||Feb 28, 2012||Richards William R||Alkaline electrolyzer|
|US8147673 *||Jun 1, 2007||Apr 3, 2012||Severn Trent De Nora, Llc||System and process for treatment and de-halogenation of ballast water|
|US8152989 *||Jun 1, 2007||Apr 10, 2012||Severn Trent De Nora, Llc||System and process for treating ballast water|
|US8156608||Apr 17, 2012||Tennant Company||Cleaning apparatus having a functional generator for producing electrochemically activated cleaning liquid|
|US8157972||Apr 17, 2012||Oxygenator Water Technologies, Inc.||Apparatus and method for improved electrolytic water treatment process|
|US8236147||Aug 7, 2012||Tennant Company||Tubular electrolysis cell and corresponding method|
|US8293085||Aug 23, 2010||Oct 23, 2012||Pionetics Corporation||Cartridge having textured membrane|
|US8319654||Jun 19, 2009||Nov 27, 2012||Tennant Company||Apparatus having electrolysis cell and indicator light illuminating through liquid|
|US8337690||Dec 25, 2012||Tennant Company||Method and apparatus for neutralizing electrochemically activated liquids|
|US8371315||Jan 25, 2010||Feb 12, 2013||Tennant Company||Washing systems incorporating charged activated liquids|
|US8377279||Nov 13, 2003||Feb 19, 2013||Siemens Industry, Inc.||Water treatment system and method|
|US8485140||Jun 5, 2009||Jul 16, 2013||Global Patent Investment Group, LLC||Fuel combustion method and system|
|US8529737 *||Mar 24, 2009||Sep 10, 2013||Tanah Process Ltd.||Portable device for regulating hardness of drinking water|
|US8551304||Feb 23, 2012||Oct 8, 2013||William R Richards||Alkaline electrolyzer|
|US8562803||Oct 6, 2006||Oct 22, 2013||Pionetics Corporation||Electrochemical ion exchange treatment of fluids|
|US8603320||Sep 16, 2011||Dec 10, 2013||Tennant Company||Mobile surface cleaner and method for generating and applying an electrochemically activated sanitizing liquid having O3 molecules|
|US8658043 *||Dec 7, 2010||Feb 25, 2014||Siemens Water Technologies Llc||Water treatment system and method|
|US8719999||Oct 17, 2011||May 13, 2014||Tennant Company||Method and apparatus for cleaning surfaces with high pressure electrolyzed fluid|
|US8747740||Jan 25, 2007||Jun 10, 2014||Hercules Incorporated||Process and apparatus for generating haloamine biocide|
|US8834687 *||Sep 28, 2006||Sep 16, 2014||Teledyne Licensing, Llc||Multilayer self-decontaminating coatings|
|US8864971||Feb 15, 2013||Oct 21, 2014||Evoqua Water Technologies Llc||Water treatment system and method|
|US8865004 *||Apr 23, 2010||Oct 21, 2014||Hydac Filtertechnik Gmbh||Device for purifying water|
|US8887668 *||Nov 8, 2012||Nov 18, 2014||Republic Of Korea (National Fisheries Research And Development Institute)||Apparatus for controlling algal blooms and killing pathogens in fish tank|
|US8894834||Dec 19, 2005||Nov 25, 2014||Evoqua Water Technologies Llc||Water treatment system and method|
|US8980079||Dec 2, 2011||Mar 17, 2015||Electrolytic Ozone, Inc.||Electrolytic cell for ozone production|
|US9011660||Jun 3, 2013||Apr 21, 2015||Evoqua Water Technologies Llc||Systems and methods for water treatment|
|US9023185||Nov 30, 2012||May 5, 2015||Evoqua Water Technologies Llc||Low scale potential water treatment|
|US9061923||Mar 4, 2013||Jun 23, 2015||Mag Aerospace Industries, Inc.||Methods and systems for disinfecting potable water supplies|
|US9090493||Oct 2, 2013||Jul 28, 2015||Pionetics Corporation||Electrochemical ion exchange treatment of fluids|
|US9097661 *||Jan 27, 2011||Aug 4, 2015||Caterpillar, Inc.||Electrochemical sulfur sensor and the method of making the same|
|US9139921||Oct 7, 2013||Sep 22, 2015||William R. Richards||Alkaline electrolyzer|
|US9162904||Mar 2, 2012||Oct 20, 2015||Tennant Company||Cleaning solution generator|
|US9180218 *||May 1, 2006||Nov 10, 2015||Teledyne Scientific & Imaging, Llc||Self decontaminating system and fabric|
|US9187347||Oct 15, 2010||Nov 17, 2015||Xogen Technologies Inc.||Treatment of a waste stream through production and utilization of oxyhydrogen gas|
|US9221695||Mar 9, 2010||Dec 29, 2015||Hansgrohe Se||Methods for decomposing partially fluorinated and perfluorinated surfactants|
|US9266733 *||Sep 30, 2005||Feb 23, 2016||Teledyne Scientific & Imaging, Llc||Multilayer self-decontaminating coatings|
|US9296629||Dec 21, 2012||Mar 29, 2016||Xogen Technologies Inc.||Treatment of a waste stream through production and utilization of oxyhydrogen gas|
|US20030062321 *||Sep 4, 2002||Apr 3, 2003||Sanyo Electric Co., Ltd.||Water treatment device|
|US20030150735 *||Nov 12, 2002||Aug 14, 2003||Kuntz Electroplating Inc.||Method and apparatus for treating an aqueous electroplating bath solution|
|US20030164306 *||Feb 21, 2003||Sep 4, 2003||Senkiw James Andrew||Microbubbles of oxygen|
|US20030216794 *||Mar 24, 2003||Nov 20, 2003||Hans Becker||Therapeutic electrolysis device|
|US20030226766 *||Jun 5, 2002||Dec 11, 2003||Orlebeke David N.||Electrolytic treatment of aqueous media|
|US20040005502 *||Jul 2, 2003||Jan 8, 2004||Harald Schlag||Conductive component for electrochemical cells and a method for its manufacture|
|US20040011652 *||Jul 16, 2002||Jan 22, 2004||Bressler Vincent Edward||Separation of particles using multiple conductive layers|
|US20040020861 *||Sep 28, 2001||Feb 5, 2004||Lehmann Nikolaj K.J.||Electrochemical cell and electrochemical treatment of contaminated water|
|US20040074781 *||Oct 22, 2002||Apr 22, 2004||Dennis Klein||Hydrogen generator for uses in a vehicle fuel system|
|US20040099599 *||Nov 19, 2003||May 27, 2004||Xogen Power Inc.||Treatment of a waste stream through production and utilization oxyhydrogen gas|
|US20040118701 *||Dec 10, 2003||Jun 24, 2004||Senkiw James Andrew||Flow-through oxygenator|
|US20050014066 *||Jun 14, 2004||Jan 20, 2005||Takayuki Shimamune||Electrode|
|US20050094484 *||Nov 26, 2002||May 5, 2005||Sextro Franz-Josef Kl.||Feeding device|
|US20050173262 *||Feb 3, 2003||Aug 11, 2005||Minoru Nakanishi||Water treatment device|
|US20050258049 *||Jan 18, 2005||Nov 24, 2005||Dennis Klein||Hydrogen generator for uses in a vehicle fuel system|
|US20060157422 *||Dec 19, 2005||Jul 20, 2006||Evgeniya Freydina||Water treatment system and method|
|US20060169645 *||Jan 31, 2005||Aug 3, 2006||Hsueh Angela M||Water treatment systems and techniques principally for use on-board aircraft|
|US20060169649 *||Nov 15, 2005||Aug 3, 2006||Hsueh Angela M||Methods and systems for disinfecting portable water supplies|
|US20070089981 *||Nov 21, 2006||Apr 26, 2007||Robert E. Moroney, Llc||Therapeutic electrolysis device|
|US20070186367 *||Jan 19, 2007||Aug 16, 2007||Tennant Company||Mobile surface cleaner having a sparging device|
|US20070186957 *||Jan 19, 2007||Aug 16, 2007||Tennant Company||Method and apparatus for producing humanly-perceptable indicator of electrochemical properties of an output cleaning liquid|
|US20070278109 *||Sep 30, 2005||Dec 6, 2007||Rockwell Scientific Licensing, Llc||Multilayer self-decontaminating coatings|
|US20070284245 *||Jun 6, 2007||Dec 13, 2007||Hegel Rudolph R||Water treatment system|
|US20080000775 *||Jun 1, 2007||Jan 3, 2008||Childers Harold E Ii||System and Process for Treating Ballast Water|
|US20080087552 *||Oct 18, 2005||Apr 17, 2008||De Nora Elettrodi S.P.A.||Cod Abatement Process For Electrochemical Oxidation|
|US20080149485 *||Jun 1, 2007||Jun 26, 2008||Childers Harold E||System and Process for Treatment and De-halogenation of Ballast Water|
|US20080179259 *||Jan 31, 2008||Jul 31, 2008||Aqua Innovations, Inc.||Flow-through oxygenator|
|US20080181815 *||Jan 25, 2007||Jul 31, 2008||Hercules Inc.||Electrochemical synthesis of haloamine biocides|
|US20080202995 *||Jan 31, 2008||Aug 28, 2008||Aqua Innovations, Inc.||Flow-through oxygenator|
|US20080210572 *||May 16, 2008||Sep 4, 2008||Tennant Company||Hand-held spray bottle having an electrolyzer and method therefor|
|US20080237060 *||Mar 26, 2008||Oct 2, 2008||Hegel Rudolph R||Methods and apparatus for electrolytic treatment of water|
|US20090032409 *||May 3, 2006||Feb 5, 2009||Juan Horn||Method for cleaning, sterilising and disinfecting dishes and other kitchen utensils and cleaning device|
|US20090068325 *||Sep 10, 2007||Mar 12, 2009||Gil Depicciotto||Method of treatment of fresh produce|
|US20090120460 *||Nov 10, 2008||May 14, 2009||Tennant Company||Soft floor pre-spray unit utilizing electrochemically-activated water and method of cleaning soft floors|
|US20090152123 *||Jul 7, 2006||Jun 18, 2009||Applied Intellectual Capital||Methods and Apparatus for Generating Oxidizing Agents|
|US20090211918 *||Mar 19, 2008||Aug 27, 2009||Industrie De Nora S.P.A.||Electrochemical cell and method for operating the same|
|US20090211919 *||Feb 2, 2009||Aug 27, 2009||Hegel Rudolph R||Apparatus and method for improved electrolytic water treatment process|
|US20090272652 *||May 5, 2009||Nov 5, 2009||Tennant Company||Charge movement detector for electrochemically activated liquids|
|US20090281480 *||Jul 5, 2006||Nov 12, 2009||David Orlebeke||Oxygenation of aqueous systems|
|US20090308738 *||Dec 17, 2009||Richards William R||Alkaline electrolyzer|
|US20090314657 *||Jun 19, 2009||Dec 24, 2009||Tennant Company||Electrolysis cell having conductive polymer electrodes and method of electrolysis|
|US20100047124 *||May 1, 2006||Feb 25, 2010||Rockwell Scientific Licensing, Llc||Self decontaminating system and fabric|
|US20100059455 *||Mar 11, 2010||Mag Aerospace Industries, Inc. D/B/A Monogram Systems||Methods and systems for disinfecting potable water supplies|
|US20100116650 *||Jul 20, 2007||May 13, 2010||Aguacure Limited||Removal of contaminants from a fluid|
|US20110042206 *||Mar 24, 2009||Feb 24, 2011||Tanah Process Ltd.||Portable device for regulating hardness of drinking water|
|US20110054572 *||Mar 3, 2011||A Major Difference, Inc.||Therapeutic electrolysis device with replaceable ionizer unit|
|US20110079520 *||Sep 30, 2010||Apr 7, 2011||Tretheway James A||Method and Apparatus for the Electrochemical Treatment of Liquids Using Frequent Polarity Reversal|
|US20110084031 *||Apr 14, 2011||Xogen Technologies Inc.||Treatment of a waste stream through production and utilization of oxyhydrogen gas|
|US20110108437 *||Jun 19, 2009||May 12, 2011||Tanah Process Ltd.||Disinfection method and disinfection device|
|US20110108489 *||Jun 10, 2010||May 12, 2011||Fritze Karl J||Integral electrolytic treatment unit|
|US20120080368 *||Apr 23, 2010||Apr 5, 2012||Richard Eberle||Device for purifying water|
|US20120111719 *||Sep 28, 2006||May 10, 2012||Teledyne Licensing, Llc||Multilayer self-decontaminating coatings|
|US20120193230 *||Aug 2, 2012||Caterpillar Inc.||Electrochemical sulfur sensor|
|US20120222953 *||Mar 2, 2011||Sep 6, 2012||Anderson Kenneth W||Systems and Methods for Producing Pressurized Gases from Polar Molecular Liquids at Depth|
|US20130032491 *||Nov 29, 2010||Feb 7, 2013||Permelec Electrode Ltd.||Membrane-electrode assembly, electrolytic cell using the same, method and apparatus for producing ozone water, method for disinfection and method for wastewater or waste fluid treatment|
|US20130284108 *||Nov 8, 2012||Oct 31, 2013||Enbion||Apparatus for controlling algal blooms and killing pathogens in fish tank|
|US20140290484 *||Mar 27, 2013||Oct 2, 2014||Cameron Solutions, Inc.||System and Method For Treating A Saline Feed Stream To An Electro-Chlorination Unit|
|USRE45415||Sep 28, 2011||Mar 17, 2015||Oxygenator Water Technologies, Inc.||Flow-through oxygenator|
|CN102224109B||Oct 15, 2009||Sep 18, 2013||昆士兰大学||Treatment method of solutions or wastewater and method for forming acid solution or alkaline solution|
|CN103270057A *||Dec 21, 2011||Aug 28, 2013||3M创新有限公司||Fluoropolymer compositions and purification methods thereof|
|CN103282551A *||Oct 13, 2011||Sep 4, 2013||六号元素有限公司||A bipolar cell for a reactor|
|DE10230395A1 *||Jul 5, 2002||Jan 15, 2004||General Motors Corp., Detroit||Leitfähiges Bauteil für elektrochemische Zellen sowie Verfahren zur Herstellung eines solchen Bauteils|
|EP2436437A1 *||Oct 20, 2009||Apr 4, 2012||Dalian Huaxinyuan Technology Development Limited Company||Anti-pollution electrocatalysis composite membrane and membrane reactor|
|EP2601143A4 *||Aug 4, 2011||Aug 5, 2015||Miox Corp||Electrolytic on-site generator|
|WO2002085794A1 *||Apr 25, 2002||Oct 31, 2002||Advanced H2O, Inc.||System for producing alkaline drinking water product|
|WO2008062170A1 *||Nov 20, 2007||May 29, 2008||Atranova Limited||Liquid treatment system|
|WO2008113841A2 *||Mar 19, 2008||Sep 25, 2008||Industrie De Nora S.P.A.||Electrochemical cell and method for operating the same|
|WO2008113841A3 *||Mar 19, 2008||Dec 24, 2008||Kenneth L Hardee||Electrochemical cell and method for operating the same|
|WO2010042987A1 *||Oct 15, 2009||Apr 22, 2010||The University Of Queensland||Treatment of solutions or wastewater|
|WO2012049512A3 *||Oct 13, 2011||Nov 1, 2012||Advanced Oxidation Limited||Bipolar cell comprising diamond sheet electrodes|
|WO2012088258A1||Dec 21, 2011||Jun 28, 2012||3M Innovative Properties Company||Fluoropolymer compositions and purification methods thereof|
|WO2014062673A1 *||Oct 15, 2013||Apr 24, 2014||M-I L.L.C.||Disinfecting water used in a fracturing operation|
|U.S. Classification||205/701, 204/255, 204/229.4, 204/229.2, 204/263, 204/275.1, 204/230.2, 204/272, 205/742, 204/228.6, 205/746, 204/228.3, 204/266, 205/758, 204/270, 204/256|
|International Classification||C02F1/42, C02F1/467, C02F1/461, C02F1/58|
|Cooperative Classification||C02F1/4672, C02F1/46104, C02F2201/46115, C02F2101/163, C02F2001/46128, C02F2201/46155, C02F1/46109, C02F2201/4611, C02F2305/026, C02F2103/30, C02F2001/46157, C02F2201/46195, C02F2303/04, C02F1/42, C02F1/4676, C02F1/4674, C02F2001/46133|
|European Classification||C02F1/461B2, C02F1/461B|
|Dec 7, 1998||AS||Assignment|
Owner name: ELECTROSYNTHESIS COMPANY, INC., THE, NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZAPPI, GUILLERMO DANIEL;WEINBERG, NORMAN L.;REEL/FRAME:009675/0536
Effective date: 19981207
|Jun 14, 2001||AS||Assignment|
Owner name: ZAPPI WATER PURIFICATION SYSTEMS, INC., NEW YORK
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:ELECTROSYNTHESIS COMPANY, INC., THE;REEL/FRAME:011891/0282
Effective date: 20010523
|Dec 31, 2002||CC||Certificate of correction|
|Jan 28, 2003||CC||Certificate of correction|
|Jun 2, 2005||REMI||Maintenance fee reminder mailed|
|Nov 14, 2005||LAPS||Lapse for failure to pay maintenance fees|
|Jan 10, 2006||FP||Expired due to failure to pay maintenance fee|
Effective date: 20051113